Process of carroting fur and the like and composition therefor



Patented July 20, 1937 UNITED STATES .IPATENT OFFICE PROCESS OF CARR/OTINGIUR AND THE LIKE AND COMPOSITION THEREFOR Constantine I. Fabian, Brookfield, Conn.,- and Alexander N.Sachanen, Woodbury, N. .L, assignors to The Non-Mercuric Carrot Company, Danbury, Conn., a corporation of Connecticut No Drawing. Original application July 1, 1936,

Serial No. 88,382. Divided and this applica tion June 4, 1937, Serial No. 146,416

-10 Claims (Cl. 8-21) This invention relates to the carroting process, nitrate, which is very active in these reactions. of fur and similar animal fibers, to give such fur The reason for the use of catalysts is the follow-- a ing:

An adequate and thorough carroting of treated animal fibers can be obtained by the use of suit!- felting properties. It iswell known thatin its natural state fur lacks adequate felting properties and must be treated with certain chemical reagents to impart thereto the required felting properties. The commonly used reagents for this purpose are nitric acid and mercuric nitrate in aqueous solution.

This application is a division of our copending application, Serial No. 88,382, filed July 1,1936. One object of the present invention is to impart to treated animal fibers strong and even felting properties without injuring the mechanical of the animal -fibers themselves. On the other strength of the treated fibers, their color or their hand, thecarroting action of moderately concencapacity to be dyed. I trated carroting solutions, which are not so dan- Another object of the invention is to avoid the gerous to animal fibers, is usually very weak and necessity of using noxious mercury salts and noxinsuflicient. That has led to the wide use oi. cataious vapors of nitric acid.

.Another object of the invention is to'avoid the increasing the carroting properties of moderately necessity of using heavy metal catalyzers which concentrated carroting solutions. It is well are apt iniuriousl'y to affect the dyeing of fur, known that in the presence of mercuric nitrate producing so-called yellow background on the felt. moderately concentrated solutions of nitric acid Another object of the invention is to combine have strong carroting properties. Processes have with thecarroting of animal fibers, in one operalso been employedutilizingcatalytically acting ation and in one carroting solution, also their substances other than mercury. cleansinating from grease and blood stains. In carrying out the present invention, use is Another object of the invention is to provide made oi. carroting solutions employlnghigh con-- means for accelerating the drying of treated fur centrations of acids and oxidizers which provide by the use of compounds with low boiling points,

permitting the use of such elevated temperatures But the use of sufliciently strong concentrations of acids and oxidizers to produce a thorough carroting has heretofore been impossible due to the strong and destructive action of such solutions upon the treated animal fibers. Such concentrated carroting solutions produce not only a carmight act deleteriously anddestructively upon as, inthe case ot treatment by the commonly used the animal fibers, such destructive action of: the

strong carroting solutions, however, being avoided or inhibited by the use 01' suitable protective agents. I

In our Patent No. 2,048,645, dated July 21, 1936,

carroting solutions, are detrimental to the animal fibers. It is well known that, as carroting is at present practised, the drying or treated skins at ordinary temperature requires anextended period of time, involving substantial expense and space requirements in the treatment 01' any considerable quantity of skins.

, protective action for the animal fibers during The carroting process comprehends complicated drying, when the concentration or the reagents chemical reactions oi the carroting reagents on becomes greater and greater and more and more detrimental to the treated fibers.

The present invention makes use of organic the animal fibers. These reactions arein general of a hydrolyzing and an oxidizing nature. For this reason, carroting solutions contain acids or substances dissolved in carroting solutions which alkalis and oxidizers dissolved in water. Adehave the property of protecting the animal fibers quate carroting of. fur can only be had by the during the carroting process as well as during the simultaneous action of a hydrolyzing agent and drying of the treated fibers and the storage an oxidizer acting each in the presence otthe thereof. other. The use of alkaline substances is usually This inventionias the use of neutral salts avoided because of the destructive action of these also) entirely eliminates the necessity oi. using substances on the animal fibers. In addition to mercury salts orother catalyticallyacting sub acids and oxidizers (in commonly used mercury stances. I I

carroting solution nitric acid is simultaneously an We' have found that organic substances suitacid and an oxidizer),"carroting solutions contam also some catalysts, as, ior instance, mercuric numerous. They should be soluble inwater'and ciently strong solutions of acids and oxidizerslysts in carroting processes for the purposeof a very strong ca'rrot'ing 'eilfe'ct and which alone able as inhibitors for carrotingv compositions are roting efiect'but also efiect a partial destruction there is disclosed and claimed the use of neutral 7 salts added to carroting solutions and providing a are oxygen, sulphur or nitrogen organic compounds.

Organic oxygen compounds--as carroting inhibitors-belong to classes: alcohols, aldehydes, ketones and carbo-acids.

Organic sulphur compounds-as carroting inhibitors-belong to classes: sulpho-acids and sulphino acids.

Organic nitrogen compounds-as carroting inhibitors-belong to classes: amines, tetrazenes and hetero-cyclic compounds containing nitrogen.

Organic substances-41s carroting inhibitors soluble in water-may be also bodies having mixed functions: e. g., aldehyde-alcohols with the groups CH0 and CHaOH, aldehyde-acids with the groups CH0 and COOH, ketone-alcohols with the groups C0 and CHaOH, ketone-acids with the groups C0 and COOH, amido-alcohols with the groups NHz and CHzOH, amido-ketones with the groups NH: and CO, amido-aldehydes with the groups NH: and CH0, amido-sulphonic acids with the groups NH: and 8031-1, etc.

These soluble in water oxygen, sulphur, nitrogen and mixed function organic compounds can be derivatives either oi! open chains or cyclic hydrocarbons.

As an example of organic compounds soluble in water, which protect the animal fibers from de structive action of concentrated carroting reagents, we may use, for instance, ethyl alcohol, ethylene glycol, glycerine, resorcinol, pyrogallol, acetone, formalin, sugar, molasses, salicylaldehyde, succinic acid, mandelic acid, lactic acid, glycolic acid, glycine, urea, triethylamine, triethanolamine, dimethylaniline, benzene-sulphonic acid, pyridine, quinoline, etc. It is understood that such organic compounds as triethylamine, pyridine, etc., are converted into corresponding salts with the acids of carroting solutions.

The quantity of used organic compounds ordinarily varies from about 4 to 10% by weight in carroting solutions.

However, for certain skins we use greater concentrations of such organic liquid substances, as ethyl alcohol or acetone. It is to be noted that these organic liquids, in addition to their protective action, have cleansing and penetrating properties. Carroting solutions with high contents of such liquids remove fat or blood ingredients 0! skins and facilitate the penetration of carroting ingredients to the treated fibers. For this reason, high concentration of such liquids in carroting solutions is recommended either for fur which is contaminated with grease and blood or for fur which has very long and dense hairs, as American Double Ring, Haresfur, etc. Both kinds of fur give with usual carroting solutions an uneven carrot due to the insufiicient penetration of carroting ingredients to fibers contaminated with fat or to fibers too long and dense. For such furs the concentration of ethyl alcohol and similar liquids in carroting solutions may be so high that the carroting process may be carried out practically in semi-aqueous or almost non-aqueous solutions which, however, are herein included under the generic term aqueous.

The organic substances, mentioned above, may be used alone or in combination with inorganic protective agents, in other words, inorganic neutral salts of the type described in our Patent No. 2,048,645, dated July 21, 1936. These salts comprise water-soluble substantially neutral salts of strong inorganic acids and strong bases, preferably salts of strong polybasic inorganic acids and alkali metals, such as bisodium sulphate and trisodium phosphate. It is obvious that this combination of two protective agents strengthens the protection of treated fibers against a destructive action of carroting reagents.

While our invention is not restricted by any theory which may be advanced to account for the precise action of the ingredients employed,- the main point being that they accomplish the results herein described-the improvement resulting in the described protective action appears to be governed by the following.

The molecules of animal fibers are oxidized not by all oxidizer molecules which are in collision with them, but only by active molecules which have a certain excess of energy in comparison with average molecules. As result of this oxidization, a certain amount of energy is liberated, and this energy activates some oxidizer molecules and enables them to further oxidize the animal fibers. For this reason, the oxidation consists of a series of consecutive oxidation and activation processes or chain reactions. The molecules of an inhibitor are able to take up the energy which is liberated in oxidation, in some way or another andto interrupt the continuous series of chain reactions.

The mechanism of the absorption of the energy liberated in oxidation in our process may be the following.

The activated molecules of the oxidizer, which have an excess of energy, react with molecules of our organic protective substances and form compounds like oxonium'salts or similar salt compounds with high valences of oxygen, nitrogen or 'sulphur. For this reason, highly activated molecules of the oxidizer lose the excess of energy and become incapable of a strong oxidation of animal fibers. Consequently the process of oxidation is carried onmoderately and practically without any descructive action on animal fibers.

We have found that our protective agent moderates and inhibits not only the oxidizing action of oxidizers, used in carroting solutions, but also the hydrolyzing action of acids used. We believe that the mechanism of this protection against an excessive hydrolyzing action of acids may be explained by the same theory of chain reactions. The hydrolysis of animal fibers is effected by certain acid molecules or hydrogen ions which are activated and have an excess of energy. This process activates other acid molecules or hydrogen ions and makes them capable of a further strong hydrolytic action, in the absence of protective substances. In the presence of such substances, the activated acid molecules or hydrogen ions give up their excess of energy to molecules of protective substances due, probably, to the formation of compounds of an oxonium type. It is well known that many alcohols and ethers form such compounds with inorganic acids.

The simultaneous action of an oxidizer, a hydrolyzing acid and the organic inhibitor, each in the presence of the other, is necessary to effect the carroting of the fur with the required inhibiting action on both the hydrolyzation and the oxidation.

As acids in our carroting solutions we use any nonoxidizing acids which give a sufiiciently strong hydrolyzing, action, for instance, sulphuric, hydrochloric, phosphoric, trichloracetic, oxalic, etc.

It is a feature of the invention that it makes possible a strong concentration of the acid as well as a relatively strong concentration of the oxidizingaction, for'instance, hydrogen peroxide, persulphates, chlorates, organic peroxides, etc.

oxidizer, which, without-the'use of the inhibitor, would'beharrnful to the fur; j For example, in the case'of sulphuric acid, when used; as the sole hydrolyzingagent, we prefer to use approximately from 5 to loidependent on the nature of the fur): of technical acid (approximately 92-93% concentration) in the case of hydrochloric acid, when used alone; approximately from 10 to 15% of technical acid (approximately 35% concentration'); and inthe case of phosphoric acid, when used alone, approximately'irom 5 to 8% (crystals In the cas'e'of the use of apluralityoi acids asubstantially similarly strong hydrolyzing effect is aimed at.

IAS oxidizers in our carroting solutions we use any oxidizers "which give a sufllciently strong Thestrengthof the oxidizing agent is} also relatively highf Forexample, in the'case oi hydro genperoxide, wfe preferto'use from 4'to 8% (dependeriton thenature of the fur) of a 30% solution." In the caseof potassium and"'ammonium persulphates or potassium chlorate we findthat" approximately from 3 to 10% (dependent on the 9 nature of the fur) on 2.100% basis gives the desired high strengthof pxidation. e

As in, the process disclosedin our Patentllo. 2,048,645, we'may and (preferably do employythe combinations of two ormore acids and two' or;

more'oxidizers. 1 i e The application of our carroting solutions to skins isjcarried out'by brushing or by spraying.

Cuthairs can be carroted also. Due tothe presence' of protective agents; skins, including the skins of white fur, carroted by our solutions may be dried at high artificial temperatures without anydetrlmental effect on" the treated animal fibers. Use may be'made in the dryer of such high temperatures as -200? F, (dependent on the nature oithe fur) which enormously facilitate and accelerate thedrying process. 'Hereto-* fore it has been impossible to dry the skins of .white fur at such elevatedftemperatures due'to a resulting .Change in color. i

The following comparative experiments demonstratethe advantageous action of the organic inhibitor. j b I i 1 hite'fur (white coney) was first carroted by a solution of hydrogenperoxide and sulphuric acid, The concentration of'each ingredient was 6% byweight. Whenj thetemperatureof dry ng" was normal, the. carroting efiect wastoo weak to make the fur available for practicalielting. The. fur required'for felting 8 rounds wetting down the initial shrinkingoperation) and 45 minutes on what is known asmachine B (commonly 1 used for effecting the final shrinkage to size and usually after dyeing); whereas for this type of fur more than 5 frounds fwetting down and more than 25 minutes on machine B is too slow felting for practical use. With the temperature of drying raised to F., thecarrot ing efiect' was better, the number of roundsbeing reduced to 6 and the time on machine B reduced to 35 that the action alone of an oxidizer and an acid on fur is either insufiicient to produce an' adequate carrot or destructive.

rot. After'drying at 175-200 IT, the number of rounds of wetting down was found to be 3 /1] and the time on machine B"'15 minutes,the' I fur being white andint-act in spite of the use of; very strong acid and oxidizer solutions.

, 10 The invention will be'better' understood by the Per cent Ammonium persulphate in aqueous solutionlr 3 Example 8 Per cent .Phosphoric acid ..,7 Hydrochloric .acid 2 Sodium sulphate 2, Pyridine 3 Ammonium persulphate 4 Potassium chlorate in aqueous solution 6 Claims directed to soluble, organic, oxygencontaining, alcoholyketone and aldehyde compounds as inhibitors are presented in the atom- Potassium chlorate L 5 Acetone in aqueous solution 8 Example} v I] fPercent Hydrochloric acid j 'i 6 v Phosphoric acid p I Hydrogen peroxide L' '8; Molasses in aqueous soiutio 8 Example 4 p i i Percent Sulphuricacid;; 6

Hydrogen peroxide u8 Ethylene -glycol- Sodium sulphate'in aqueous solution 4 Example 5 I Percent.

: Benzene-jsulphonic acid 5 Potassium chlorate in aqueous solution; 5

Example. 6

i i Percent ,Sodium sulphate- 2 Triethanolamineinnu; 4-

: Potassium persulphate 3% Hydrogen peroxide in aqueous solution -s 6 Example 7 [Ethyl alcohol"; -L

said co-pending application, Serial No. 88,382.

Claimstosoluble, organic, nitrogen-containing made as the same have been heretofore exemplified, all within the scope of our generic invention, it being understood that the matter hereinbefore set forth is submitted as illustrative and not in a limiting sense. I

We'claim:

. 1. An aqueous carroting solution for treating fur and the like containing an oxidizing agent and an acid hydrolyzer, and containing also an inhibitor comprising a water-soluble, organic, oxygen-containing, carbo-acid compound present in amount to prevent harmful action on the fur of the oxidizing agent and the hydrolyzer, said solution being substantially free from heavy metal catalytic agents.

2. An aqueous carroting solution for treating fur and the like containing an oxidizing agent and an acid hydrolyzer, and containing also an inhibitor comprising a water-soluble, organic, oxygen-containing, glycolic acid compound present in amount to prevent harmful action on the fur'of the oxidizing agent and the hydrolyzer,

said solution being substantially-free from heavy metal catalytic agents.

3. An aqueous carroting solution for treating fur and the like containing an oxidizing agent and an acid hydrolyzer, and containing also an inhibitor comprising a water-soluble, organic, oxygen-containing, succinic acid compound present in amount to prevent harmful action on the fur of the oxidizing agent and the hydrolyzer, said solution being substantially free from heavy metal catalytic agents.

4. An aqueous carroting solution for treating fur and the like containing an oxidizing agent and an acid hydrolyzer, and containing also an inhibitor comprising a water soluble, organic,

oxygen-containing, mandelic acid compound present in amount to prevent harmful action on the fur of the oxidizing agent and the hydrolyzer, said solution being substantially free from heavy metal catalytic agents. 7

5. An aqueous carroting solution for treating fur and the like containing an oxidizing agent and an acid hydrolyzer, and containing also an inhibitor comprising a water-soluble, organic; oxygen-containing, carbo-acid compound present in amount to prevent harmful action on the fur of the oxidizing agent and the hydrolizer, there being present in the solution also a watersoluble, neutral salt of a strong inorganic acid and a strong base, said solution being substan tially free'from heavy metal catalytic agents, v

6. An aqueous carroting solution for treating fur and the like containing an oxidizing agent and an acid hydrolyzer, and containing also an inhibitor comprising a water-soluble, organic,

,oxygemcontaining, carbo-acid compound present in amount to prevent harmful action on the fur of, the oxidizing agent and the hydrolyzer, the acid hydrolyzer being present in the solution in a concentration of an order represented by from 5 to 10% of technical sulphuric. acid of approximately 92%, said solution being substanfur of the oxidizing agent and the hydrolyzer,

the acid hydrolyzer being presentin the solution in a concentration of an order represented by from 5 to 10%. of technical sulphuric acid of approximately 92%, andthere being present in the solution also a water-soluble, neutral salt of a strong inorganic acid and a strong base in an amountv less than that of the acid, said solution being substantially free from heavy metal catalytic agents.

8. The process of preparing fur and the like for felting, which comprises treating the fur with an aqueous carroting solutioncontaining an oxidizing agent and an acid hydrolyzer, said solu-- tion being substantially free from heavy metal catalytic agents, checking the carroting action of such solution by an inhibitor comprising a water-fsoluble, organic, oxygen-containing, 'carbo-acid compound present inthe solution in amount to prevent harmful action on the miof the oxidizing agent and the hydrolyzer, and causing such solution to dry on the fur.

9. The process of preparing fur and the like for felting, which comprises treating the fur with an aqueous carroting solution containing an oxi- 'dizing agent and an acid hydrolyzer, said solution being substantially free from heavy metal catalytic agents, checking the carroting action of such solution by an inhibitor comprising a water-soluble, organic, oxygen-containing, succinic acid compound present in the solution in amount to prevent harmful action on the fur of the oxidizing agent and the hydrolyzer, and causing such solution to dry on the fur.

10. The process of preparing fur and the like.

for, felting, which comprises treating the fur with anaqueouscarroting solution containing an oxidizing-agent and an acid hydrolyzer, the latter present in the solution in a concentration of an order represented by from 5 to 10% of technical sulphuric acid of approximately 92%, said solution being substantially free from heavy metal catalytic agents, checking the carroting action of such solution by an inhibitor comprising a water-soluble, organic, oxygen-containing, carboacid compound present in the solution in amount to prevent harmful action on the fur of the oxidizingagent and the hydrolyzer, and causing such solution to dry on the fur.

CONSTAN'IINE F. FABIAN. ALEXANDER N. SACHANEN. 

